KR20150050948A - Etchant composition for Cu/Mo alloy film - Google Patents

Etchant composition for Cu/Mo alloy film Download PDF

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Publication number
KR20150050948A
KR20150050948A KR1020130132239A KR20130132239A KR20150050948A KR 20150050948 A KR20150050948 A KR 20150050948A KR 1020130132239 A KR1020130132239 A KR 1020130132239A KR 20130132239 A KR20130132239 A KR 20130132239A KR 20150050948 A KR20150050948 A KR 20150050948A
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South Korea
Prior art keywords
molybdenum
copper
hydrogen peroxide
etchant composition
compound
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KR1020130132239A
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Korean (ko)
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이창호
윤영철
박충우
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솔브레인 주식회사
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Priority to KR1020130132239A priority Critical patent/KR20150050948A/en
Publication of KR20150050948A publication Critical patent/KR20150050948A/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

Provided is an etchant composition for a thin copper/molybdenum film, which does not contain a fluorine compound, does not cause a problem of molybdenum residue, and has an excellent number of processed wafers. The etchant composition comprises: hydrogen peroxide; an organic or inorganic acid; an azole compound; an amine compound; a chelating agent; and a hydrogen peroxide stabilizer.

Description

구리/몰리브데늄 합금막의 식각액 조성물{Etchant composition for Cu/Mo alloy film}[0001] The present invention relates to an etching composition for a copper / molybdenum alloy film,

본 발명은 불소 화합물을 포함하지 않는 구리/몰리브데늄 박막용 식각액 조성물에 관한 것이다. The present invention relates to an etchant composition for a copper / molybdenum thin film containing no fluorine compound.

최근에는 박막 트랜지스터 액정표시장치의 전기적 신호 지연을 감소시키기 위해 낮은 저항값을 지니며 환경적으로도 큰 문제가 없는 금속배선재로 구리(Cu)가 각광받고 있다. 하지만 구리는 유리막과의 접착력(adhesion)이 좋지 않고 실리콘 층과의 Cu의 확산 (diffusion) 을 예방하기 위하여 다양한 barrier metal을 사용하게 된다. 그 중 현재 각광 받고 있는 barrier metal은 몰리브데늄이다. In recent years, copper (Cu) has been attracting attention as a metal wiring material having a low resistance value in order to reduce the electrical signal delay of a thin film transistor liquid crystal display device and having no environmental problems. However, the adhesion of copper to the glass layer is poor and various barrier metals are used to prevent the diffusion of Cu into the silicon layer. One of them is molybdenum.

구리와 몰리브데늄을 효과적으로 식각하기 위해서는 일반적으로 과수계 식각액을 사용한다. In order to effectively etch copper and molybdenum, a hydro-etchant is generally used.

과산화수소 식각엑에서 구리는 pH가 낮을수록, 몰리브데늄은 pH가 높을수록 식각이 잘된다. 하지만 pH가 높은 영역에서는 과산화수소의 안정성이 나쁘기 때문에 일반적으로 과산화수소 식각액의 pH는 1 ~ 3 이다. 이 pH의 영역대에서 불소화합물을 사용하지 않으면 몰리브데늄의 잔사(Residue)가 발생하여 판넬 제조 공정에 불량을 야기시킨다. 이를 방지하기 위해서 불소 화합물을 사용한다. 하지만 불소 화합물을 함유함에 따라 유리기판의 식각을 야기하여 판넬 제조 공정 중 불량 발생시 유리기판의 재사용을 제한하는 문제점을 지니고 있다.The lower the pH of the etching solution is, the higher the etching rate of molybdenum is. However, since the stability of hydrogen peroxide is poor in the high pH range, the pH of the hydrogen peroxide etching solution is usually 1 to 3. If a fluorine compound is not used in the region of this pH, a residue of molybdenum is generated and causes a defect in the panel manufacturing process. To prevent this, a fluorine compound is used. However, the glass substrate is etched due to the inclusion of a fluorine compound, thereby restricting the reuse of the glass substrate when a defect occurs in the panel manufacturing process.

또한, 불소 화합물을 사용하지 않고 몰리브데늄을 원할히 식각하기 위해서 식각액의 pH 영역을 4~7로 조절하여야 Further, in order to uniformly etch molybdenum without using a fluorine compound, the pH range of the etching solution should be adjusted to 4 to 7

한다. 하지만 pH가 높은 경우에는 과산화수소의 안정성이 매우 좋지 않다. 또한 구리 및 몰리브데늄을 식각하면서 전이금속인 구리와 몰리브데늄이 과산화수소 식각액에 녹으면 안정이 매우 좋지 못하여 구리 기준으로 1000ppm도 사용할 수 없을 정도로 공정 마진이 없다. do. However, when the pH is high, the stability of hydrogen peroxide is not very good. In addition, when copper and molybdenum are etched in copper and molybdenum, transition metals such as copper and molybdenum are dissolved in the hydrogen peroxide etching solution, which is not very stable and there is no process margin to such an extent that copper can not be used at 1000 ppm.

본 발명은 불소 화합물을 포함하지 않고 몰리브데늄의 잔사 문제가 없으며 처리 매수 능력도 우수한 구리/몰리브데늄 박막용 식각액 조성물을 제공하는 데 목적이 있다.An object of the present invention is to provide an etchant composition for a copper / molybdenum thin film which does not contain a fluorine compound and has no problem of residual molybdenum, and which is also excellent in the ability to remove impurities.

본 발명은 1)과산화수소, 2)유기산 또는 무기산, 3)아졸계 화합물, 4)아민 화합물 및 킬레이트제 및 과산화 수소 안정제를 포함하는 구리/몰리브데늄 박막용 식각액 조성물을 제공한다. The present invention provides an etching solution composition for a copper / molybdenum thin film comprising 1) hydrogen peroxide, 2) an organic acid or an inorganic acid, 3) an azole compound, 4) an amine compound and a chelating agent and a hydrogen peroxide stabilizer.

본 발명에 따른 구리/몰리브데늄 박막용 식각액 조성물은 불소 화합물을 포함하지 않고 몰리브데늄의 잔사 문제가 없으며 처리 매수 능력도 우수하다. The etchant composition for a copper / molybdenum thin film according to the present invention does not contain a fluorine compound and has no problem of residual molybdenum, and has excellent ability to remove impurities.

불소 화합물을 사용하지 않는 구리/몰리브데늄 박막용 에칭액은 아래와 같이 구성된다.The etching solution for a copper / molybdenum thin film which does not use a fluorine compound is constituted as follows.

(1) 과산화수소 (2) 구리를 식각할 수 있는 유기산 혹은 무기산 (3) 식각 속도를 조절 할 수 잇는 아졸계 화합물 (4) pH 조절 할 수 있는 아민 화합물 (5) 구리 와 몰리브데늄을 킬레이트 할 수 있는 킬레이트제 (6) 과산화수소의 안정성을 높여주는 pH가 높은 과산화수소 안정제 (7) pH가 4 ~ 7 인 불소 화합물을 사용하지 않는 구리/몰리브데늄 박막용 에칭액은 아래와 같이 구성된다.(4) pH-controllable amine compounds; (5) chelates copper and molybdenum; and (5) amines capable of controlling pH. (6) Hydrogen peroxide stabilizer with high pH, which enhances the stability of hydrogen peroxide. (7) The etching solution for copper / molybdenum thin film, which does not use fluorine compound and pH 4 ~ 7, is composed as follows.

(1) 과산화수소 (2) 구리를 식각할 수 있는 유기산 혹은 무기산 (3) 식각 속도를 조절 할 수 잇는 아졸계 화합물 (4) pH 조절 할 수 있는 아민 화합물 (5) 구리 와 몰리브데늄을 킬레이트 할 수 있는 킬레이트제 (6) 과산화수소의 안정성을 높여주는 pH가 높은 과산화수소 안정제 (7) pH가 4 ~ 7 인 구리/몰리브데늄 합금막의 식각액 조성물을 제공한다.(4) pH-controllable amine compounds; (5) chelates copper and molybdenum; and (5) amines capable of controlling pH. (6) a hydrogen peroxide stabilizer having a high pH which increases the stability of hydrogen peroxide; and (7) a copper / molybdenum alloy film having a pH of 4 to 7.

본 발명은 불소 화합물을 사용하지 않고, pH 4 ~ 7인 식각액으로 몰리브데늄의 잔사 문제가 없고 처리매수 능력도 구리 기준으로 4,000ppm 이상으로 공정 손해가 없다. 또한 일반적인 불소를 포함하논 pH 1 ~3의 식각액과 동등 수준의 식각 속도 및 프로파일(Profile)을 가진다.In the present invention, molybdenum residue is not caused by an etchant having a pH of 4 to 7 without using a fluorine compound, and the processing ability of copper is not less than 4,000 ppm based on copper. It also has the same etch rate and profile as the etchant at pH 1 to 3, including normal fluorine.

pH 4 ~ 7의 영역대에서 안정적이고 처리매수 능력을 갖추기 위하여, 피로인산 나트륨 등 몇 가지 과수안정성을 가진 첨가제를 사용할 수 있다.In order to be stable and able to acquire the processing ability at a pH range of 4 to 7, additives with some fruit stability such as sodium pyrophosphate can be used.

pH 4~7의 영역대에서 아민 화합물을 사용하여서 pH 맞추었을 때 잔사가 없다. There is no residue when the pH is adjusted using an amine compound in the range of pH 4 to 7.

발명 1Invention 1 불소 화합물Fluorine compound 비교 1Comparison 1 비교 2Comparison 2 비교 3Comparison 3 산화제Oxidant H2O2 6H2O2 6 H2O2 6H2O2 6 H2O2 6H2O2 6 H2O2 6H2O2 6 H2O2 6H2O2 6 식각액Etchant 숙신산 5Succinic acid 5 황산 0.5Sulfuric acid 0.5 숙신산 5Succinic acid 5 숙신산 5Succinic acid 5 숙신산 5Succinic acid 5 아졸 화합물Azole compound ATZ 0.1ATZ 0.1 ATZ 0.1ATZ 0.1 ATZ 0.1ATZ 0.1 ATZ 0.1ATZ 0.1 ATZ 0.1ATZ 0.1 아민화합물Amine compound 에탄올아민Ethanolamine 2 2 -- -- 에탄올 아민 2Ethanolamine 2 에탄올 아민 1Ethanolamine 1 킬레이트제Chelating agent IDA 1IDA 1 IDA 1IDA 1 IDA 1IDA 1 IDA 1IDA 1 IDA 1IDA 1 안정제stabilizator 피로인산나트륨Sodium pyrophosphate 3 3 피로인산나트륨Sodium pyrophosphate 3 3 -- 피로인산나트륨Sodium pyrophosphate 3 3 불소화합물Fluorine compound -- HFHF 0.1 0.1 -- -- -- 기타 첨가제Other additives -- TMAH 3TMAH 3 TMAH 3TMAH 3 pHpH 5 ~ 5.55 ~ 5.5 1 ~ 1.51 to 1.5 5 ~ 5.55 ~ 5.5 5 ~ 5.55 ~ 5.5 3 ~ 3.53 ~ 3.5 Cu 식각Cu etching 좋음good 좋음good 좋음good 좋음good 좋음good Mo 식각Mo etching 좋음good 좋음good 잔 사Sleeping 좋음good 잔 사Sleeping 처리매수Number of processing Cu 6,000ppmCu 6,000 ppm Cu 6,000ppmCu 6,000 ppm Cu 6,000ppmCu 6,000 ppm Cu 1,000ppmCu 1,000 ppm Cu 6,000ppmCu 6,000 ppm Si damageSi damage 없 음none 있 음has exist 없 음none 없 음none 없 음none 전체 평점All Ratings 매우 좋음Very good 나쁨Poor 나 쁨Bad 나쁨Poor 나쁨Poor

Claims (1)

1)과산화수소, 2)유기산 또는 무기산, 3)아졸계 화합물, 4)아민 화합물 및 킬레이트제 및 과산화 수소 안정제를 포함하는 구리/몰리브데늄 박막용 식각액 조성물1) hydrogen peroxide, 2) an organic or inorganic acid, 3) an azole-based compound, 4) an etchant composition for a copper / molybdenum thin film comprising an amine compound and a chelating agent and a hydrogen peroxide stabilizer
KR1020130132239A 2013-11-01 2013-11-01 Etchant composition for Cu/Mo alloy film KR20150050948A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108893741A (en) * 2018-06-12 2018-11-27 江苏理工学院 A kind of floride-free copper-molybdenum etching solution applied to thin film transistor line
US10377948B2 (en) 2016-11-29 2019-08-13 Samsung Electronics Co., Ltd. Etching composition and method for fabricating semiconductor device by using the same
WO2020042223A1 (en) * 2018-08-31 2020-03-05 深圳市华星光电技术有限公司 Etching solution composition for copper/molybdenum film layer
WO2020042234A1 (en) * 2018-08-31 2020-03-05 深圳市华星光电技术有限公司 Efficient copper-molybdenum etching solution and etching method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10377948B2 (en) 2016-11-29 2019-08-13 Samsung Electronics Co., Ltd. Etching composition and method for fabricating semiconductor device by using the same
US10800972B2 (en) 2016-11-29 2020-10-13 Samsung Electronics Co., Ltd. Etching composition and method for fabricating semiconductor device by using the same
CN108893741A (en) * 2018-06-12 2018-11-27 江苏理工学院 A kind of floride-free copper-molybdenum etching solution applied to thin film transistor line
WO2020042223A1 (en) * 2018-08-31 2020-03-05 深圳市华星光电技术有限公司 Etching solution composition for copper/molybdenum film layer
WO2020042234A1 (en) * 2018-08-31 2020-03-05 深圳市华星光电技术有限公司 Efficient copper-molybdenum etching solution and etching method

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